Fungicidal cyclopentanones



2,972,563 FUNGICIDAL CYCLOPENTANONES Sidney B. Richter, Chicago, 111.,

Chemical Corporation, Chicago, of Illinois No Drawing. Filed Jan. 13,1959, Ser. No. 786,45d

Claims. (Cl. 167 -30) assignor to Velsicol 111., a corporation Thisinvention relates to new compositions of matter.

' More specifically, this invention relates to chemical compounds of thegeneral formula wherein x is a whole number from 0 to 3 and R can be anunsubstituted phenyl, monohydroxyphenyl, monochlorophenyl, ordichlorophenyl radical. These new compounds have been found to beunusually active as pesticides, particularly as fungicides.

The compounds oi this invention can .be prepared readily by thecondensation of hexachloro-Z-cyclopento none with the appropriateprimary amine (x and R are as defined above). The reaction can becarried out with only two moles of amine for each table material can beprepared by heating octachlorocyclo-' pentene with concentrated sulfuricacid as described by Newcomer and McBee, J. Am. Chem. Soc., vol. .71, p.946 (1949). The primary amines also required for the reaction are eitherchemicals of commerce or can be prepared readily by those skilled in theart. The primary amine to be used in the reaction is selected on thebasis of the identity desired for x and R in the final product. Thus, inorder to obtain compounds according to this invention in which x is 0,amines such as aniline, o-chloroaniline, m-chloroaniline,p-chloroaniline, 2,4-dichloroaniline, 3,4-dichloroaniline,2,6-dichloroaniline, o-aminophenol, m-aminophenol, p-aminophenol, andthe like are used. Compounds in which x is l are obtained by usingbenzylamine or its derivatives such as o-chlorobenzylamine,2,6-dichlorobenzylamine, e-amino-o-cresol, and the like. Compounds inwhich x is 2 are obtained by using phenethylamine or its derivativessuch as p-chlorophenethylamine, 2,4-dichlorophenethylamine, orp-hydroxyphenethylamine (tyramine). In a like manner, compounds in whichx is 3 are obtained by using B-phenylpropylamine or its chlorinated andhydroxylated derivatives.

Compounds according to this invention in which R is an unsubstitutedphenyl radical are obtained by using the primary amines wherein R is anunsubstituted phenyl 2,972,563 Patented Feb. 21, 1961 "ice . 2 group:aniline, benzylamine, .phenethyl-amine, and 3; phenylpropylamine.Compounds in which R is a monochlorophenyl radical are obtained by usingsuch amines as o-chloroaniline, m-chloroaniline, p-chloroaniline, m-

chlorobenzylamine, p-chlorophenethylamine,3-(o-chlorophenyl)'propylamine, and the like. Compounds in which R is adic hlorophenyl radical are obtained by using such amines as2,4'dichloroaniline, 2,5-dichloroaniline, 3,4- dichloroanilinc,3.5-dichloroanilinc, 2,6-dichloroaniline, 2,6 -dichlorobcnzylaminc, 2,4dichlorophcncthylamine, and the like. Similarly, compounds in which R isa monohydroxyphcnyl radical are obtained by using such amines aso-aminophenol, m-aminophenol, p-aminophenol, a-amino-o-cresol,p-hydroxyphenethylamine, and the like.

The manner in which typical compounds of this invention can be preparedis illustrated in the following examples.

EXAMPLE 1 Preparation of the benzylimine Hexachloro-Z-cyclopentenone,M.P. 28 C., was prepared as described by Newcomer and McBee, J. Am.Chem. Soc., 71, 946 (1949). This ketone (29 g.; 0.1 mole) was dissolvedin 140 ml. benzene in a SOD-ml. round-bottomed flask fitted with amechanical stirrer, reflux condenser, and dropping funnel. Benzylamine(22 g.; 0.2 mole) in 80 ml. benzene was added dropwise with stirringover a period of 70 minutes. The mixture was stirred at room temperaturefor 1 hour and then at reflux for 1 hour. The cooled' solution wasfiltered, washed with water, and dried over calcium chloride. Thesolution was concentrated to about half its volume by distillation ofpart of the benzenein vacuo, and the concentrate was treated withheptane to precipitate 20 g. of product (55% of theory). Severalrecrystallizations of the product from heptane gave pure3-benzylimino-2,2,4,4,5- pentachlorocyclopentanone, melting point113-1l6 C.

Analysis for C H Cl NO.-Theory: C, 40.09%; H, 2.23%; Cl, 49.33%. Found:C, 39.90%; H, 2.23%; Cl, 49.27%.

EXAMPLE 2 Preparation of the p-hydroxyphenylimine p-Aminophenol(43.6.g.'; 0.4 mole) in 400 ml. dioxane was added dropwise with stirringover a period of 1 hour to hexachloro-2-cyclopentenone .(58 g.; 0.2mole) dis-- Preparation of the o-chlorophenylimine A mixture ofhexachloro-2-cyclopentenone (29 g.; 0.1

mole), o-chloroaniline (25.5 g.; 0.2 mole), and 220 ml.

benzene was refluxed for 22.5 hours in a 500-ml., roundbottomed fiaskfitted with a reflux condenser. The solvent was then distilled frorh themixture in vacuo to give a liquid residue which solidified to a darkpurple solid on standing at room temperature for a week. The solid wasextracted with ether, leaving an insoluble salt. The ether was distilledfrom the extract in vacuo to leave a solid residue, which wasrecrystallized from heptane and treated with Nuchar in acetone solution.The acetone was dis- 3 tilled off in .vacuo to leave a yellow solid,which was recrystallized several times from heptane to give 13 g. (34%of theory) of light tan 3-0-:hlorophenylimino-2,2,4,4,5-

pentachlorocyclopcntanone, melting point i54-167 C.

.A wide variety of other useful compounds within the scope of thisinvention can be prepared in the manner detailed in the above examples.Given in the following ex' amples are the particular primary aminesrequired for reaction with hexachloro-2-cyclopentenone (identifiedhereinafter as A) to give the indicated typical compounds of thisinvention.

EXAMPLE 4 2,4-dic hloroanilinc+A-:3-(2,4-dichlorophcnylimino2,2,4,4,5-pentachlorocyclopentanone.

EXAMPLE 5 m-Chlo roaniline +A=3-m-chlorophenylimino-2,2,4,4,5-pentaehlorocyclopentanone.

EXAMPLE 6 o-Aminophenol+A==3-o-hyrdoxyphenylimino-2,2,4,4.5-pentachlorocyclopentanone.

EXAMPLE 7 p-Chloroaniline+A=3-p-chlorophenylimino 2,2,4,4,5-pentachlorocyclopentanone.

EXAMPLE 8 3,S-dichloroaniline-i-A=3-(3,5 dichlorophenylimino)-2,2,4,4,5-pentachlorocyclopentanone.

EXAMPLE 9 m-Aminotahenol-l-A=3-m-hydroxyphenylimino-2,2,4,4- I

S-pentachlorocyclopentanone.

EXAMPLE 1 2,5-dichloroaniline-i-A=3 2,5-dichlorophenylimino)2,2,4,4,5-pentachlorocyclopentanone.

EXAMPLE 11 oChlorobenzylamine+A=3-o-chlorobenzylimino 2,2,4,4,5-pentaehlorocyclopentanone.

EXAMPLE 12 3,4-dichlorobenzylamine+A==3 (3,4dichlorobenzylimino)-2,2,4,4,S-pcntachlorocyclopentanone.

EXAMPLE 13 wAmino-o-cresol+A=3-o-hydroxybenzylimino 2,2,4,4.5-pentachlorocyclopentanonc.

EXAMPLE l4 p-Chlorophenethyiamine+A=3-p-chlorophenethylimino-2,2,4,4,S-pentachlorocyclopentanone.

EXAMPLE l 2,4-dichlorophenethylamine+A=3-(2,4-dichlorophenethylimino)-2,2,4.4,5-pcntachlorocyclopentanone.

EXAMPLE l6 p-Hydroxyphenethylamine+A=3 p-hydroxyphenethylimino-2,2,4,4,5-pentachlorocyclopentanone.

EXAMPLE [7 3-phenylpropylarnine-l-A=3- (3-phenylpropylimino)-2,2,4,4,S-pentachlorocyclopentanone.

EXAMPLE l9 Aniline+A=3 phenylimino 22.4.4.5

pentachlorocyclopentanone.

4 EXAMPLE 20Phenethylamine-l-A:3-phenethylimino-2,2,4,4,5-pentachlorocyclopentnnone.

The new compounds of this in ention have been found to be unusuallyactive as pesticides, particularly as fungicides. For example, thetoxicity of candidate compounds to test spores was determined by theslide germination technique adopted by the Committee on Standardizationof Fungicidal Tests of the American 'Phytopthological Society. Measuredconcentrations of spores were placed on glass slides in contact withvarious concentrations of the compound being tested. Three replicateswere run at each concentration. The percentage germination of spores wasthen determined for each treatment after 24 hours incubation at 72 F.Typical results are recorded in the following table.

bean rust on bean foliage. Pinto bean seedlings, grown under greenhouseconditions, were mounted on a special compound turntable and sprayedwith the test compounds at various concentrations for 30 seconds at 30pounds pressure. The plants were allowed to dry, inoculated with sporesuspensions of the bean rust organism, Uromyces phascoli, and placed inan incubation chamher for 24 to 48 hours. The plants were then removed,maintained under greenhouse conditions for 10 to 14 days, after whichthe number of rust postules on the leaves of each plant were thendetermined. Three replicates were run at each concentration. Typicalresults are recorded in the table below.

Pesticidal compositions of this invention are prepared by mixing one ormore of the new compounds of this invention with inert carriers ,toprovide formulations adapted for ready and efiicient application withconventional applicator equipment to the site of the pest infestation.For example, pesticidal compositions or formulations according to thisinvention are prepared in the form of solids or liquids. Solidcompositions are preferably in the form of dusts. These are prepared togive homogeneous, free-flowing dusts by admixing the active compound orcompounds of this invention with finely divided solids such as thetales, natural clays, pyrophyllite, diatomaceous earth, Fullers earth,or flours such as walnut shell, wheat, redwood, soya bean, or cottonseedflours. Other inert solid carriers of the type ordinarily used inpreparing pest control compositions in dusts or powdered form can alsobe used.

.Liquid compositions according to this invention are prepared byadmixing One or more of the new compounds of this invention with asuitable inert liquid diluent. In some cases the compounds aresufiicient y active agents can be of the anionic, cationic ornonionictypes. Typical examples of such surface-active agents are sodiumstearate, potassium laurate, morpholine oleate, sodium lauryl sulfate,sodium Z-ethylhcxyl-sulfate, sodium naphthalenesulfonate, sodiumalkylnaphthnlenesulfonate, sodium sulfosuccinate, sodium oleic acidsulfonate, sodium castor oil sulfonate, glycerol monostearate containinga soap (or a sodium fatty alcohol sulfate), lithium stearate, magnesiumoleate, aluminum stearate, methyl cellulose, sodium salt ofligninsulfonic acid,

polyoxyethylene fatty alcohol ethers, polyglycol fatty I acid esters,polyoxyethylene modified fatty acid esters, polyoxyethylene-polyol fattyacid esters, polyoxypropylene fatty alcohol ethers, polypropylene glycolfatty acid esters, polyoxypropylene modified fatty acid esters,polyoxypropylenepolyol fatty acid esters, polyol fatty acid monoesters,lecithin, .diand higher polyhydric alcohol fatty acid esters,cholesterol andother fatty acid esters,-

lanolin, oxidized fatty oils, quaternary ammonium salts such as lauryldimethyl benzyl ammonium chloride, amine hydrochlorides such aslaurylamine hydrochloride, alkylated aryl polyether alcohols such as thecondensation product of diamylphenol with ethylene oxide, and the like.Mixtures of such agents can be used to com bine or modify properties.The proportion of these agents will ordinarily vary from about 1% orless to about by weight of the pestieidal compositions. Other pesticidesas well as such substances as fertilizers, activators, adhesives,spreaders, and synergists can be added to the formulations if desired.The manner in which typical pesticidal compositions according to thisinvention can be prepared is illustrated in the following examples. Allquantities given are in parts by weight.

EXAMPLE 21 Preparation of an emulsifiable concentrate The followingingredients are blended thoroughly until a homogeneous liquidconcentrate is obtained. This concentrate is mixed with water to give anaqueous dispersion containing the desired concentration of activecompound for use as a spray.

3 benzylimino 2,2,4,4,5 pentachlorocyclopentanone Sodium lauryl sulfate2 Sodium lignin sulfonate 3 Kerosene 70 EXAMPLE 22 Preparation of aweltable powder 3-p-hydroxyphenylimino 2,2,4,4,5pentachlorocyclopentanone 75.00 Fullers earth 22.75 Sodium laurylsulfate 2.00 Methyl cellulose .25

EXAMPLE 23 Preparation of an oil-dr'spersible powder The followingcomponents are blended and ground as described in the previous exampleto give a powder which can be dispersed in oil to form a spraycontaining the desired concentration of active compound.

3-0 chlorophenylimino 2,2,4,'4,5 pentachlorocyclopentanone 70Condensation product of diamylphenol with 'ethylene oxide Fullers earEXAMPLE 24 L inoculum before it reaches the site of infection.

Preparation of a dust -The following ingredients are mixed thoroughlyand then ground to an average particle size of less than about 50microns to give a dust suitable for application with conventionaldusting equipment.

3 (2,4 dichlorophenethylimino) 2,2,4,4,5- pentachlorocyclopentanone 20Talc 80 EXAMPLE 25 Preparation of a granular formulation The followingingredients are mixed with sufiicient water to form a paste, which isthen extruded, dried, and ground to give granules, preferably from about5 to A inch in diameter. The granules are applied with fertilizerspreader equipment or other conventional apparatus. The dextrin in thisformulation serves as a binding agent.

3 (3 phenylpropylirnino) 2,2,4,4,5 Q pentachlorocyclopentanone J 1Fullcrs earth 66 Dextrin 20 Sodium lignin sulfnnate V 3 Kerosene 1.nature of the disease, and the nature of the plant attacked. They maybe used as preventive agents to form a toxic barrier between theinoculum and the host tissue, to inhibit the production of inoculum, orto destroy the They may be used as eradicating agents to destroy thedisease-producing organism or its inoculum on the host tissue or in thesoil. They may be used as curatives or therapeutic agents to destroy thedisease-producing organisms within the plant tissues, halt their growth,or inhibit the development of their toxins or counteract them. They mayalso be used as'prophylactic agents to immunize plants against disease.can be useful in any one or more of the above ways, but since it is mucheasier to protect plants from dis ease rather than to cure disease, thechemicals are best used in the form of .protectants. These protectivechemicals can act to prevent sporulation and thus reduce or eliminatethe inoculum necessary for the spread of a disease. They can alsoprevent spores from completing their germination or incubation stage sothat no infection ensues. These eradicant chemicals, which can also beconsidered broadly as protectants, are used to destroy of fungal growthon wood, plastics, textiles, and like ma- I terials.

When used for the control of plant diseases, the compounds of thisinvention can be used as seed treatments,

' soil treatments, or plant treatments. Many of the disease-producingbacteria and the fungi that cause blights, spots, and rots are carriedon or in seeds, roots, bulbs,

The compounds of this inventiontubers, corms, or other seed stock thatis purchased by growers. These disease-producing organisms can bedestroyed by dipping the seed or planting stock in liquid formulationsof the compounds of this invention. Many plant pathogens are alsosoil-borne, and the application of the active compounds to the soil isone of the useful methods for control or eradication of the organisms,particularly in greenhouses, cold frames, hot beds, and seedbeds. Bothsolid and liquid compositions of the compounds of this invention can beused in such soil treatments. Plant treatments by chemicals in the formof liquid or solid fungicidal compositions are made on growing crops oron crop residues either to prevent the appearance or spread of diseasesor to destroy the disease-causing organisms already present or both.This type of treatment is essential for plant protection from air-bornepathogenes and is also useful in controlling many seedand soil-bornepathogenes that spread externally to the upper parts of plants. Suchtreatment ineludes the application ofthe active chemicals internally toprevent or destroy diseased conditions. The active compounds of thisinvention are applied by any of these methods in amounts sufficient toexert the desired pesticidal action. The amount of the active compoundpresent in the pesticidal compositions as actually applied fordestroying or preventing pest infestations varies with the type ofapplication, the particular pests which are to be controlled, thepurpose for which the treatment is made, and the like. Generally, thesolid or liquid pesticidal compositions of this invention will containfrom about 0.5% to about 90% of the active compounds.

I claim:

1. A method of destroying undesirable fungi on growing plants whichcomprises contacting said fungi with a fungicidal composition comprisingan inert carrier and as the essential active ingredient, in a quantitywhich is toxic to said pests, a compound of the formula wherein x is awhole number from 0 to 3 and R is selected from the group consisting ofunsubstituted phenyl, monohydroxyphenyl, monochlorophenyl, anddichloropheny-l radicals.

2. A method as described in claim I, wherein R is an unsubstitutedphenyl radical.

A method as described in claim 1, wherein R is a monohydroxyphenylradical.

4. A method as described in claim 1, wherein R is a monochlorophenylradical.

5. A method as described in claim 1, wherein R is a dichlorophenylradical.

6. A method as described in claim 1, wherein the compound is3-benzy1imino-2,2,4,4,S-pentachlorocyclopentanone.

7. A method as described in claim 1, wherein the compound is3-p-hydroxyphenylimino-2,2,4,4,5-pentachlorocyclopentanone.

8. A method as described in claim 1, wherein the compound is3-o-chlorophenylimino-2,2,4,4,5-pentachlorocyclopentanone.

9. A method as described in claim 1, wherein the compound is3-(2,4-dichlorophenethylimino)-2,2,4,4,5-pentachlorocyclopentanone.

10. A method as described in claim I, wherein the compound is 3 (3phenylpropylimino)-2,2,4,4,5-pentachlorocyclopentanone.

References Cited in the file of this patent Newcomber et al.: J.A.C.S.vol. 71, PP- 946-951 (1949).

1. A METHOD OF DESTROYING UNDESIRABLE FUNGI ON GROWING PLANTS WHICHCOMPRISES CONTACTING SAID FUNGI WITH A FUNGICIDAL COMPOSITION COMPRISINGAN INERT CARRIER AND AS THE ESSENTIAL ACTIVE INGREDIENT, IN A QUANTITYWHICH IS TOXIC TO SAID PESTS, A COMPOUND OF THE FORMULA